Light-sensitive silver halide photographic material

ABSTRACT

A light-sensitive silver halide photographic material containing as anti-spotting agent, at least one compound represented by the general formula

United States Patent [191 Ushiyama et al.

[ Dec. 11, 1973 LIGHT-SENSITIVE SILVER HALIDE PHOTOGRAPIIIC MATERIAL[73] Assignee: Konishiroku Photo Industry Co.,

Ltd., Tokyo, Japan 221 Filed: Sept. 11, 1972 21 Appl. No.: 288,160

Related US. Application Data [63] Continuation-impart of Ser. No.39,568, May 21,

1970, abandoned.

[30] Foreign Application Priority Data May 28, 1969 Japan 44/40991 [52]US. Cl. 96/74, 96/94 R, 96/1145, 260/513 [51] Int. Cl. G03c l/38, G03c1/40, G03c l/04 [58] Field of Search 96/74, 94 R, 114.5; 260/513 [56]References Cited UNITED STATES PATENTS 3,003,877 10/1961 McLaughlin96/1145 3,084,187 4/1963 Gaerther 260/513 3,165,409 l/l965 Knox 96/94Primary Examiner-J. Travis Brown Assistant Examiner-Alfonso T. S'uroPico AttorneyEric H. Waters et al.

[57] ABSTRACT A light-sensitive silver halide photographic materialcontaining as anti-spotting agent, at least one compound represented bythe general formula e 1 N/CH mCHC OOM 4 Claims, No Drawings ILIGHT-SENSITIVE SILVER HALIDE PHOTOGRAPHIC MATERIAL CROSS REFERENCE TORELATED APPLICATION This application is a continuation-in-partapplication of Ser. No. 39,568 filed May 21, 1970 now abandoned.

The present invention relates to light-sensitive silver halidephotographic materials containing a novel antispotting agent forpreventing so-called spots (white or black stains) which are formed onthe surfaces of lightsensitive silver halide photographic materialsafter development due to such causes as dusts, heavy metal powders orthe like which are present in the air.

It has been known that certain kinds of dusts or fine particles of heavymetals which are present in the air become causes for formation of spotson the surfaces of light-sensitive photographic materials. It isconsidered that spots are formed when such dust-like materials havemigrated into light-sensitive photographic materials during theproduction thereof. In order to inhibit the formation of spots, whichinjure the photographic properties of light-sensitive materials, it isan ordinary practice to remove dust like materials present in theatmosphere surrounding the steps for production of lightsensitivephotographic materials. However, the removal of dust-like materials inthe air is quite difficult and is substantially impossible, in practice,because they are generated during the steps for production oflight-sensitive materials or brought into the steps to gether withstarting materials for the production thereof. It has therefore beendesired to prevent the influence on photographic properties of thedust-like materials which have undesirably been contained inlightsensitive photographic materials. In order to accomplish this,there have been adopted processes in which anti-spotting agents areincorporated into layers constituting light-sensitive photographicmaterials such as, for example, silver halide emulsion layers, interlayers, sub layers or protective layers. However, the conventionalanti-spotting agents are not satisfactory yet, and have the disadvantageof undesirably reacting with other photographic additives presenttogether therewith or with the developers.

A principal object of the present invention is to overcome theabove-mentioned drawbacks of the conventional anti-spotting agents andto provide light-sensitive photographic materials having excellentphotographic properties.

As the result of extensive studies, we have found that compoundsrepresented by the general formulas l and II are excellent anti-spottingagents and that lightsensitive photographic materials incorporated withsaid compounds have such excellent characteristics that they are notaffected at all by dust or fine powders of such heavy metals as iron,copper, tin, lead, chromium and nickel and oxides thereof which arepresent in the air, and they are not degraded in inherent photographicproperties.

G eneral formula I:

General formula ll:

wherein:

R and R aliphatic, aromatic, alicyclic or heterocyclic groups, which maybe optionally substituted;

R an alkyl or substituted alkyl group;

R R R and R]: hydrogen atoms or methyl groups, but R and R and R and Rcannot be methyl groups at the same time;

Y: an divalent organic residue;

M and M hydrogen atoms, alkali metals, ammonium or organic amine salts;

p: a positive integer of l to 6; and

m: 0 or 1.

Typical examples of the compounds represented by the above-mentionedgeneral formulas are set forth below, but it is needless to say thatcompounds usable in the present invention are not limited only to these.

IIC4I'IQOCII'JCIICI'I2N/ OH CH2COONa CH2=CHCHzOOHzCHCH2N OH CIIZCHQCOOK(3) CH2CH(CH3)COOH HOCHQCIIZOCI'IZCHCIIQN )I'I CHZCOOH CHQCOOK CHCOOKOCH2CHCHzN )H CH2C OOK 5 ongooom nC-tHoOCHzCHCHzN OH CHZCOOH (6)CHzGHzCO OH HOGIIECHCHQOCHZCHCHZN )13: OH CH2CH2SO H CHzCOOHCHzOCHzCHzOOI-IzOHCHzN )H CIIQCIICH20II (8) H H2 H2 H CHZCII2COONII-lCH3 OCHzCHCHzN H H OH CH2CH2PO(ONH )3 (9) l cmormooon O CH2OCH2(]3HCH2N\OH CH2PO(OH)2 (10) .CII CH CH S 03K n-CrHq-Q-O CH2CHCH2N OH lCH2COOK 110o c-c11zcH2 15 rcooccng KO 0 C CH2 II N N H CHzCOOK (16) CHzCOONILCHzCOONH4 CHzCOOK CHzCHzC OOH .CHQQQQM Synthesis Example 1 The compoundof exemplification 5 is synthesized in such a manner as described below.

54 g. of iminodiacetic acid, 200 ml. of water and 42.4 g. of anhydroussodium carbonate are dissolved together to neutral pH, and the resultingsolution is heated. Into this solution is added 52 g. of rectifiednbutyl glycidyl ether. After completion of the dropping, the resultingmixture is reacted at 90C. for 4 hours. Subsequently, the mixture iscooled, adjusted to pH 3.2 to 3.4 by addition of 1:1 hydrochloric acidand then concentrated over a water bath. The concentrate is dissolved in200 ml. of ethanol at an elevated temperature and then subjected tofiltration. The filtrate is concen- CH2COOK CHZCOOK l isoCdl oCIIzClIClIzN-CH2CIICHZNCHZCIICHZO C4HylSO II II H (17) OH OH 0112011011200011 trated, and the concentrate is dissolved in 220 ml. of 3 00methanol at an elevated temperature and then filtered. 011,011 HCHQCHCOOH The filtrate obtained is again concentrated, and the CHconcentrate is refluxed over a water bath together with 250 ml. of ethylacetate, followed by cooling and filtra- 19 CHZCI'IZSCHI; tion. Theresulting crystals are dried to obtain 71 g. of CHF O OH2CHCH2N J:HC00N8pale yellow, hygroscopic crcystals, m.p. 163C.

lmtaranaior (BH omooom E e s. yis HHZONOhNa z C (70 H N 0 Calculated44.91 7.14 4.76 (20 /CHzCOONa Found 4501 7.19 4.81 OGH2fi3HCH:N\ Whenthe above procedure is repeated, except that n M 0H OHNOOH allylglycidyl ether is used in place of the n-butyl glyci- (|)H CHQCOONaNaOOCCHz C| H c1120 CHZOHCI'IZN NCHzCHCHzOCH CHzCOONa NaOOCCHz NaO 0 0CH2 OH NCHzCHCHzO CH OH CHzOOONa NaOOGCHz E H OCH: HCHZN NaO 0 0 OH: OH

c1120 0 ONa NCHaCHCHaOCH OH CHZC 0 0N2. M10 0 0 CH2 1 CH2OCH2CHCI'I2N\ gCHzCOONa The above-mentioned anti-spotting agents are synthesized, forexample, according to the procedures set forth in the followingsynthesis examples:

dyl ether, there is obtained the compound of exemplification l3 in theform of pale yellowish brown, hygroscopic crystals, m.p. 45C.

Synthesis Example 2 filtration. The filtrate is Concentrated, and theconcentrate is formed into a sodium salt by addition of a mixturecomprising 300 ml. of water and 14 g. of anhydrous sodium carbonate,followed by concentration. The concentrate is precipitated from ethanolto obtain 2.3 g. of white crystals.

Elementary analysis for C l-l NNaO c H N Calculated 49.78 8.36 5.81Found 49.54 8.50 5.69

Synthesis Example The compound of exemplification 16 is synthesized asdescribed below.

9 g. of N-isobutyloxyglycerine-sodium glycinate is dissolved in 80 ml.of water and the resulting solution is added with 6 g. of anhydroussodium carbonate. Further, 2.6 g. of glycerol-1,3-dichlorhydrin is addedthereto and the total mixture is heated on a water bath for 6 hours.After cooling, 13 ml. of HCl aq. (1:1) is added to make the pH value ofthe reaction mixture to 3.0 The mixture is concentrated and theyellowish brown concentrate obtained is taken into 200 ml. of 80 percentmethanol. After filtration and concentration, the residual mass iswashed with 50 ml. of acetone and 100 ml. of ether. After decantation,washing with 100 ml. of acetone is effected and the remaining mass isconcentrated under reduced pressure. A viscous pale yellow product itobtained. By dissolving in excess am moniac water and thenconcentrating, an yellow viscous product which is identified as theexemplified compound 16 on page 6 of the specification is obtained. Thishas thefollowing elementary analysis:

C H N Calcd. 48.64 9.67 18.18 Found 48.58

Other compounds employed in the present invention can also besynthesized according to the abovementioned synthesis procedures. Thethus obtained compounds of the aforesaid general formulas may be usedeither singly or in admixture, and are incorporated into silver halideemulsion layers in an amount within the range of 1 X to l X 10" mols permol of silver halide, or are incorporated into sub layers, inter layersor protective layers in an amount within the range of 5 X 10' to l X 10mols per square meter, whereby the formation of spots due to dusts,heavy metals or oxides thereof in the air or due to other causes can beeffectively prevented. If necessary, the compounds may be added in anamount out of the above-mentioned ranges.

Ordinarily, the extent of spot formation varies de' pending on the pHvalues of silver halide emulsions, and some of the known anti-spottingagents have a tendency to be varied in anti-spotting action clue tovariation in PH of silver halide emulsions. However, the.

aforesaid compounds employed :in the present invention do notsubstantially vary in effectiveness at a pH range of ordinary silverhalide emulsions, regardless of whether they are acidic or alkaline. andhence are markedly effective. Further, the compounds employed in thepresent invention are not injured. Moreover, the effects of thecompounds are not dominated by the kind of supports and of materials ofsub layers, and thus the compounds are effectively applied to all thelightsensitive silver halide photographic materials such as usualblack-white and color films specific specif lightsensitive printing andX-ray materials.

The present invention is illustrated in further detail below withreference to examples, but it is needless to say that the presentinvention is not limited to these examples.

Example 1 An ordinary speed ortho-type photographic emulsion comprisingg. of silver bromide was subjected to gold sensitization at the time ofsecond ripening, incorporated with the usual additives, and divided intotwo portions A and B. Emulsion A was incorporated with 0.5 g. of thecompound of exemplification l0 and then coated on a polyester support toprepare a sample A. On the other hand, emulsion B was coated as it wason a polyester support to prepare a sample B. After setting, each samplewas sprinkled with a nickel powder, dried, cut and then subjected todevelopment. As a result, a large number of spots were formed in sampleB, whereas no formation of spots was observed in sample A.

Example 2 A high speed regular type photographic emulsion comprising 100g. of silver bromide was subjected to gold sensitization at the time ofsecond ripening, incorporated with the usual additives, and divided intotwo portions C and D. Emulsion C was coated as it was on a polyestersupport to prepare a sample C. On the other hand, emulsion D wasincorporated with l g. of the compound of exemplification 5 and thencoated on a polyester support to prepare a sample D. Each sample wassprinkled with dust collected from the air and then dried, out andsubjected to development. As a result, a large number of spots wereformed in sample C, whereas no formation of spots was observed in sampleD. Further, no degradation in photographic and physical properties wasobserved in sample D.

Example 3 A high speed panchromatic type photographic emulsioncomprising 100 g. of silver iodobromide was subjected to goldsensitization at the time of second ripening, and then incorporated withthe usual additives. Subsequently, the emulsion was coated on acellulose triacetate support, and then set and divided into two portionsto prepare samples E and F. Sample E was coated with an aqueous gelatinesolution containing 2 g. of the compound of exemplification 14 to form aprotective film thereon. On the other hand, sample F was coated with anaqueous gelatine solution. Each sample was sprinkled with dust collectedfrom the air and then dried, out and subjected to development. As aresult, no formation of spots and no degradation in photographic andphysical properties were seen in sample E, whereas a large number ofspots were formed in sawmi l- A sub-coating liquid for a polyestersupport was divided into two portions G and H. Portion G wasincorporated with 3 g. of the compound of exemplification l5 and thencoated on a polyester support, followed by drying, to prepare a sampleG. On the other hand, portion H was coated as it was on a polyestersupport, followed by drying, to prepare a sample H. Each sample wascoated with a low speed regular type silver iodobromide photographicemulsion and, after setting, the

sample was sprinkled with iron powder, dried, cut and subjected todevelopment. As a result, no formation of spots was observed in sampleG, whereas a large number of spots were formed in sample H.

Example 5 A silver chlorobromide photographic emulsion, after secondripening, was incorporated with the usual additives and divided into twoportions of] and J. Emulsion l was incorporated with 0.1 g. of thecompound of exemplification 8 and coated on a baryta paper to prepare asample I. On the other hand, emulsion J was coated as it was on a barytapaper to prepare a sample .1. After setting, each sample was sprinkledwith chromium powder, dried, cut and subjected to development. As aresult, no formation of spots was observed in sample 1, whereas a largenumber of spots were formed in sample J.

A comparison of the anti-spotting activity of compounds according to theinvention with structurally similar compounds of the prior art are givenin the two examples which follow.

Example 6 Compound A (F.P. 1,581,866)

l O H Compound B (according to the invention) CIhCOONaClhzClIClhOClhCIIClI N on CHaCOONa A high speed light-sensitive silverhalide photographic emulsion (1 Kg.) comprising 100 g. of silveriodobromide was subjected to gold sensitization at the time of secondripening, incorporated with usual additives, and divided into threeequal portions of A, B and C. The emulsions A and B were incorporatedwith 0.5 g. of the above compounds A and B, respectively, and thencoated on a polyester support to prepare samples A and B. On the otherhand, the emulsion C was coated as it was on a polyester support toprepare a sample C. After setting, each sample was sprinkled with aniron powder, dried, cut and then subjected to development. As a result,a large number of spots were formed in samples A and C, whereas no spotformation was observed in sample B. The results are tabulated below.

Compound Amount No. of Sample used (g./%Kg. emulsion) spots/dm ACompound A 0.5 g. 80 B Compound 8 0.5 g. 2 C 98 Example 7 Compound D(U.S.P. 3,084,187)

OH: CI I3 O CI'I2CHCH2NOHzCHzSOQN;

Compound E (according to the invention) CIhCOONa C H OCHiCHCHiN OHCHaCOONa A high speed light-sensitive silver halide photographicemulsion comprising 100 g. of silver iodobromide was subjected to goldsensitization at the time of second ripening, incorporated with usualadditives, and divided into three equal portions of D, E and F. Theemulsions D and E were incorporated with 0.5 g. of the above compound Dand E, respectively and then coated on a polyester support to preparesamples D and E. On the other hand, the emulsion F was coated as it wason a polyester support to prepare a sample F. After setting, each samplewas sprinkled with an iron powder, dried, out and then subjected todevelopment. As a result, a large number of spots were formed in samplesD and F, whereas no spot formation was observed in sample E. The resultsare tabulated below.

Compound Amount No. of Sample used (g./%Kg. emulsion) spots/dm DCompound D 0.5 g. E Compound E 0.5 g. 3 F 97 We claim:

C H mCHCOOM R1O CH7CHCH1-N l a 1, 4 CH mCHCOOM R1-OCHiCHCH2 R1'O CHgCHCHr-N wherein:

R and R are aliphatic, aromatic, alicyclic or heterocyclic groups, whichmay be optionally substituted;

R is an alkyl or substituted alkyl group;

R R R and R are hydrogen atoms or methyl groups, but R and R and R and Rcannot be methyl groups at the same time:

Y is a divalent organic residue;

M and M are hydrogen atoms, alkali metals ammonium or organic aminesalts;

P is a positive integer of l to 6; and

m is 0 or 1.

2. A light-sensitive silver halide photographic material as claimed inclaim 1, wherein said emulsion layer is a color former-containing colorphotographic emulsion layer.

3. A light-sensitive silver halide photographic material as claimed inclaim 1, wherein said anti-spotting agent has been incorporated into asilver halide emulsion layer in the amount of l X 10 to l X 10 mole permole of silver halide contained in said silver halide emulsion layer.

4. A light-sensitive silver halide photographic mate- 10 mole per squaremeter of the layer concerned.

2. A light-sensitive silver halide photographic material as claimed inclaim 1, wherein said emulsion layer is a color former-containing colorphotographic emulsion layer.
 3. A light-sensitive silver halidephotographic material as claimed in claim 1, wherein said anti-spottingagent has been incorporated into a silver halide emulsion layer in theamount of 1 X 10 4 to 1 X 10 1 mole per mole of silver halide containedin said silver halide emulsion layer.
 4. A light-sensitive silver halidephotographic material as claimed in claim 1, wherein said anti-spottingagent has been incorporated into a sub layer; inter layer or protectivelayer in the amount of 5 X 10 6 to 1 X 10 2 mole per square meter of thelayer concerned.